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179

DakinWest reaction
The direct conversion of an D-amino acid into the corresponding D-acetylaminoalkyl methyl ketone, via oxazoline (azalactone) intermediates. The reaction proceeds in the presence of acetic anhydride and a base such as pyridine with the evolution of CO2.

O
R

CO2H

Ac2O

CO2n

NH2
R

NHAc
O

CO2H

NH2

OH

HN

O
O

H+
O
R

O H
O
O

OH
O

AcO
H

AcO
H
O
R

OH

OH

O OH

oxazolone (azalactone) intermediate

O
R
HN

O
H

CO2

tautomerization
N

OH

NHAc

Example 112

Me

CO2H
NH2

Ac2O, AcOH, Et3N


o

DMAP, 50 C, 14 h, > 90%

Me

Me
NHAc

180

Example 214

HO
O
N
H

Ac2O, pyr.

O
OBn

90 oC, 2 h, 58%

O
N
H

Me
O
OBn

References:
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Dakin, H. D.; West, R. J. Biol. Chem. 1928, 78, 91, 745, and 757. In 1928, Henry Dakin and Rudolf West, a clinician, reported on the reaction of D-amino acids with acetic
anhydride to give D-acetamido ketones via azalactone intermediates. Interestingly,
one year before this paper by Dakin and West, Levene and Steiger had observed both
tyrosine and D-phenylananine gave abnormal products when acetylated under these
conditions.2,3 Unfortunately, they were slow to identify the products and lost an opportunity to be immortalized by a name reaction.
Levene, P. A.; Steiger, R. E. J. Biol. Chem. 1927, 74, 689.
Levene, P. A.; Steiger, R. E. J. Biol. Chem. 1928, 79, 95.
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